Inorganic Syntheses, VolumeI

Edited by Harold Simmons Booth

Copyright © 1939 by McGraw-Hill Book Company, Inc.

TRZOXALATOS A L T S 35

ward the amount of carbon consumed may be estimated by

noting the position of the hottest point.
The resulting gas is dried by passing it over P20s. The
impurities consist principally of C2F6 and higher fluorides
as well as some O2 and OF2 (from unreacted Fz and NaOH
solution). Complete separation of CF, from the impurities
can be attained by fractional distillation in a modern
column.2 It is difficult to remove the last traces of C2Fs
by ampoule-to-ampoule distillation alone. At liquid-air
temperatures, the nearly pure substance, as well as the
unpurified product, liquefies to a colorless liquid containing
varying amounts of a white precipitate (C2F6), the amount
depending on the purity.
Properties
Pure CF4 melts at -183.6’ and boils at -127.8”. The
heat of vaporization is 2947 cal. ; and the heat of formation,
about 183,500 cal. S0298= 63 eal. per degree, AFoZg8=
- 173,500 cal. from C and Fz. The gas is very unreactive.
It does not attack glass even at elevated temperatures. It
reacts with metallic sodium only when the mixture is heated.
References
1. RUFF and KEIM:2. anorg. allgem. Chem., 192, 249 (1930); RUFFand
217, I (1934).
BRETSCHNEIDER.
2. BOOTH Znd. Eng. Chem., 29,470 (1937).
and BOZARTH:

13. TRIOXALATO SALTS

(Trioxalatoaluminiate, -ferriate, -chromiate,
and -cobaltiate)

SUBMITTEDBY JOHNC. BAILAR, JR.,*AND ELDONM. JONES*

CHECKED BY H. 8. BOOTHt AND M. GRENNERTt

Many different types of complex metal oxalates have been

described, the best known being the trioxalato salts of the
* University of Illinois, Urhana, Ill.
t Western Reserve University, Cleveland, Ohio.
36 INORGANIC SYNTHESES

trivalent metals containing the ion [M(Cz0J3]”’,in which

M may represent any one of a number of trivalent ions.
The amount ’ of water of hydration is variable, but salts
containing the same number of molecules of water often
form isomorphous series.
Bergmann and Fox1 have recently shown that potassium
trioxalato chromiates and cobaltiates preeipitate glycine
specifically from mixtures of amino acids.
Of the many methods available for the preparation of
the trioxalato salts, a few are illustrated here.
A. POTASSIUM TRIOXALATOALUMINIATE

&[A1(C20,) 31.3H20
Al(OH)3 + 3KHCz04 + K3[Al(C204)3].3HzO

A solution of 67 g. (0.1 mol) of aluminum sulfate,

A1z(S04)3-18Hz0,is treated with a solution of 24 g. of
sodium hydroxide. The precipitated aluminum hydroxide
is filtered, washed, and boiled with a solution of 76.8 g.
of potassium hydrogen oxalate (or a mixture of 55.2 g.
of potassium oxalate monohydrate and 37.8 g. of oxalic
acid dihydrate) in about 800 ml. of water. Any aluminum
hydroxide which does not dissolve is filtered out and the
filtrate is evaporated to crystallization. The yield is nearly
quantitative.
B. POTASSIUM TRIOXALATOFERRIATE

K3[Fe(Cz04)3].3Hz0
+
Fez(S04)3 3BaCz04+ Fez(C204)3 3BaS04 +
Fez(CzOJ3 + +
3KzCz04 6Hz0 4 2K@”(Cz04)3]-3HzO

Twenty-five grams of ferric sulfate, 50 g. of barium

oxalate (which may be prepared from 50 g. of BaClz.2HzO
and 29.3 g. of NazC2O4),and 27.3 g. of potassium oxalate
monohydrate are placed in 600 ml. of water and digested
for several hours on the steam bath. After filtering with
suction and washing the precipitate, the filtrate is evapo-
 TRIOXALATO SALTS 37

rated to 100 ml. and allowed to cool. The light-green

trioxalatoferriate crystallizes in nearly quantitative yield.
Any soluble ferric salt, in the presence of excess oxalate
ion, yields the trioxalatoferriate. By using ferric sulfate
and barium oxalate the elimination of foreign ions is rendered
very easy.
.
C POTASSIUM TRIOXALATOCOBALTIATE3

K3[Co(Cz04)31.3HzO
HzC204 + H2O CO2 T
cOc03 -+ c O c z 0 4 + +
+ +
2COczO4 4KzCz04 PbOz 4HCzH302 4 +
+ +
2K3[Co(CzOJJ 2KCzH30z Pb(CzH30z)z 2HzO +
Twenty-three and eight-tenths grams (0.2 mol) of cobalt
carbonate is dissolved in a solution of 25.2 g. of oxalic
acid (HzC204*2Hz0)and 73.7 g. of potassium oxalate
(K2CzO4-H20) in 500 cc. of hot water. When the solution
has cooled to 40°C., while it is vigorously stirred, 23.9 g.
of lead dioxide (see synthesis 16) is added slowly, followed
by 25 ml. of glacial acetic acid added a drop at a time.
The stirring is continued for an hour, during which time
the color changes from red t o deep green. After the
unused lead dioxide is filtered out, the trioxalatocobaltiate is
precipitated by the addition of 500 mi. of alcohol. The
material appears as emerald-green needles, which are
sensitive to both light and heat; The yield is 70 g. (71 per
cent).
D. POTASSIUM TRIOXALATOCHROMIATE2

K~[Cr(C204)~1.3H~O.
KzCrzO, + 7HzC204 + 2KzC204 2K3[Cr(Cz04)3].3Hz0
+ +
--f

6C02 HzO
To a solution of 23 g. of potassium oxalate monohydrate
a.nd 55 g. of oxalic acid dihydrate in 800 ml. of water is
added 19 g. of powdered potassium dichromate in small
portions with vigorous stirring. When the reaction is
ended, the solution is evaporated nearly to dryness and
38 INORGANIC S Y N T H E S E S

allowed to crystallize. Potassium .trioxalatochromiate

forms deep-green crystals with a brilliant blue iridescence.
Yield 45 g. (90 per cent). -
References
and Fox: J . Biol. Chem., 109, 317 (1935).
1. BERGMANN
2. GRAHAM:
Ann., 29, 9 (1839).
2. anorg. Chem., 11, 2 (1896).
3. SORENSEN:

14. SILICOBROMOFORM (TRIBROMOSILANE)

+
Si 3HBr + SiHBrB Hz +
+
(Si 4HBr .+SiBrl 2Hz) +
+
(Si 2HBr -+ SiHzBrz)
BY W. C. SCHUME~*
SUBMITTED
BY R. C. YOUNG*
CHECKED

Silicobromoformis usually prepared by passing hydrogen

bromide over heated ~ i l i c o n or
~ ,a~silicide
* ~ ~ ~such as copper
~iIicide.~The product, consisting of a mixture of silicon
tetrabromide with a few per cent of tri- and dibromosilanes,
is purified by shaking with mercury, if necessary, to remove
any free bromine, and by fractional distillation. The use
of metal silicides instead of silicon does not add appreci-
ably to the yield of the bromoform and is not recommended
in the following procedure.
Procedure
The apparatus is assembled as shown in Fig. 6 and is
constructed throughout of pyrex glass. Hydrogen gas
is passed through several towers A of fused potassium
hydroxide,t thence through the rest of the system to sweep
out the air. The bubble tube B contains bromine, warmed
in a water bath to 45°C. The hydrogen when allowed to
bubble through the bromine forms a mixture which is
passed through the catalyst tube C containing platinized
* Massachusetts Institute of Technology, Cambridge, Mass.
t The commercial fused potassium hydroxide is best remelted in a nickel
crucible and poured out upon a cold surface (such as a copper sheet), and
when solidified and cooled somewhat, is broken up into flakes suitable for
charging the absorption towers.